CN113786820A - Functionalized ferroferric oxide particle and preparation method and application thereof - Google Patents
Functionalized ferroferric oxide particle and preparation method and application thereof Download PDFInfo
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- CN113786820A CN113786820A CN202111180948.6A CN202111180948A CN113786820A CN 113786820 A CN113786820 A CN 113786820A CN 202111180948 A CN202111180948 A CN 202111180948A CN 113786820 A CN113786820 A CN 113786820A
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- ferroferric oxide
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 239000002245 particle Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 33
- 239000002344 surface layer Substances 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 9
- -1 amino, imino Chemical group 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- 239000004593 Epoxy Substances 0.000 claims abstract description 5
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 69
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 24
- 239000000725 suspension Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002351 wastewater Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 150000001298 alcohols Chemical class 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 150000002576 ketones Chemical class 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000003828 vacuum filtration Methods 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 239000003002 pH adjusting agent Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- 239000011247 coating layer Substances 0.000 abstract description 6
- 238000007885 magnetic separation Methods 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000005389 magnetism Effects 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 description 22
- 235000019441 ethanol Nutrition 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 9
- 239000002105 nanoparticle Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000009920 chelation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a functionalized ferroferric oxide particle and a preparation method and application thereof, wherein the functionalized ferroferric oxide particle consists of a magnetic ferroferric oxide core and a polymer chain net surface layer, and active groups on the polymer chain net surface layer comprise hydroxyl, amino, imino and epoxy; the functionalized ferroferric oxide particle has a chelating surface layer and a ferroferric oxide core at the same time, and has excellent heavy metal chelating and trapping capacity and excellent magnetic separation performance; the functionalized ferroferric oxide particle surface is a polymer chain network, the magnetism cannot be weakened due to the over-thick coating layer, the separation is easy, and the recovery operation is simple and convenient; and the preparation method is simple and is beneficial to industrial popularization and application.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to functionalized ferroferric oxide particles and a preparation method and application thereof.
Background
In the past decades, with the vigorous development of science and technology, industry and agriculture, the Chinese economy has changed greatly, and also causes huge energy consumption and serious pollution to the environment, especially the heavy metal pollution problem in water resources is increased. Heavy metal pollutants, which are generally considered to be the most common toxic pollutants in soil and water systems, can enter the food chain by biologically amplifying the toxic substances, and finally, can transfer the enriched heavy metals to the human body, even if a small amount of heavy metals enter the human body, which can cause serious harm to the human body. Seriously damaging the ecological environment, human health and causing serious economic losses. Therefore, it is important to control the heavy metal content in water resources, and the rational utilization of water resources seems to be one of the most urgent environmental problems in the world.
The current practices for removing heavy metal ions from wastewater include ion exchange, chemical precipitation, electrochemistry, coagulation-flocculation, oxidation, chelate precipitation, membrane filtration, photocatalytic degradation, electrodialysis, and adsorption processes. The adsorption method has the advantages of low cost, simple design, convenient operation, wide application range and the like, and is favored by many researchers when treating heavy metal ions in wastewater. Therefore, it is one of the focus and research directions of the present sewage treatment field to prepare an economically applicable adsorbent to obtain a higher sewage treatment effect and to seek a more efficient and environmentally friendly treatment method.
CN103319212B discloses a preparation method of a filtering material with functions of adsorbing and fixing arsenic and heavy metals, which comprises the steps of adsorbing divalent iron ions on a porous ceramic matrix, carrying out in-situ reduction on the divalent iron ions adsorbed on the porous ceramic matrix by using a reducing agent, and finally carrying out anaerobic sintering on the porous ceramic matrix at 400-500 ℃, wherein the porosity of the porous ceramic matrix is 35-85%, and at least 25 wt% of ceramic components forming the porous ceramic matrix is diatomite. The filter material obtained by the invention forms a nose-like porous and villus filter structure on a microstructure and generates an adsorption film, thereby greatly improving the adsorption efficiency and adapting to the change of water quality chemical environment. The used filtering material does not fall off or separate out heavy metals, and the use safety is good. However, the adsorption speed of the invention is slow, the separation and recovery after adsorption are difficult, and the recycling performance is poor.
CN110615510A discloses an amino-functionalized magnetic ferroferric oxide nano particle and a preparation method thereof. The nano particle consists of ferroferric oxide nano particles (magnetic cores) with the average size of 20-40nm and an amino functional coating layer with the thickness of 1-3nm, wherein the amino functional coating layer is formed on the surface of the ferroferric oxide nano particles by hydrolysis and condensation of 3-aminopropyl triethoxysilane (APTES). The preparation method of the nano-particles comprises the following steps: 1) ferric trichloride, sodium hydroxide and deionized water are heated in ethylene glycol to prepare ferroferric oxide nano particles as magnetic nuclei; 2) dispersing the magnetic core obtained in the step 1) into an aqueous solution, and directly adding 3-Aminopropyltriethoxysilane (APTES) for amino functional modification to obtain amino functional magnetic ferroferric oxide nanoparticles. The method has simple and environment-friendly process, does not need a silicon dioxide transition layer, and does not need to use an organic solvent and adjust the pH value of the solution. The obtained amino functionalized magnetic ferroferric oxide nano particles are uniform in coating, regular in structure, high in magnetic substance content and good in dispersity, and can be used as an adsorbent for removing pollutants in water. Although the adsorbing material disclosed by the invention can realize magnetic separation, the magnetic property of the ferroferric oxide nanoparticles can be influenced to a certain extent by the completely covered coating layer on the surface.
Therefore, the development of the adsorbent with high adsorption efficiency, strong magnetism, convenient separation and recovery and long cycle service life has important significance for improving the removal effect of the heavy metal ions in the wastewater and promoting the treatment of the heavy metal wastewater.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide functionalized ferroferric oxide particles and a preparation method and application thereof, wherein the functionalized ferroferric oxide particles consist of a magnetic ferroferric oxide core and a polymer chain net surface layer, and active groups on the polymer chain net surface layer comprise hydroxyl, amino, imino and epoxy; the functionalized ferroferric oxide particle has a chelating surface layer and a ferroferric oxide core at the same time, and has excellent heavy metal chelating and trapping capacity and excellent magnetic separation performance; the functionalized ferroferric oxide particle surface is a polymer chain network, the magnetism cannot be weakened due to the over-thick coating layer, the separation is easy, and the recovery operation is simple and convenient; and the preparation method is simple and is beneficial to industrial popularization and application.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the purposes of the invention is to provide functionalized ferroferric oxide particles, wherein the functionalized ferroferric oxide particles consist of a magnetic ferroferric oxide core and a polymer chain net surface layer; the active groups on the surface layer of the macromolecular chain net comprise hydroxyl, amino, imino and epoxy.
The functionalized ferroferric oxide particle disclosed by the invention takes magnetic ferroferric oxide as an inner core, and the surface of the magnetic ferroferric oxide particle is a macromolecular chain net containing abundant active groups of hydroxyl, amino, imino and epoxy, so that the functionalized ferroferric oxide particle has excellent heavy metal chelating and trapping capacity and magnetic separation performance, greatly improves heavy metal trapping and adsorbing capacity, effectively solves the problems that an adsorbing material is complicated to separate and cannot be continuously operated after adsorbing heavy metals, can realize efficient heavy metal removal and continuous adsorption and separation operation, and is convenient for industrial popularization and application.
The second object of the present invention is to provide a method for preparing functionalized ferroferric oxide particles according to the first object, wherein the method comprises the following steps:
(1) mixing ferroferric oxide, glycolic acid, carbon disulfide, ammonium citrate and a solvent to obtain a suspension;
(2) and (2) dropwise adding epoxy chloropropane into the suspension obtained in the step (1) to react, and sequentially carrying out solid-liquid separation, washing and drying to obtain functionalized ferroferric oxide particles.
In a preferred embodiment of the present invention, the mass ratio of glycolic acid to ferroferric oxide in step (1) is (0.1-0.5):1, and may be, for example, 0.1:1, 0.15:1, 0.2:1, 0.25:1, 0.3:1, 0.35:1, 0.4:1, 0.45:1, 0.5:1, etc., but the present invention is not limited to the above-mentioned values, and other values not listed in the above-mentioned range of values are also applicable.
The mass ratio of the glycolic acid to the ferroferric oxide is (0.1-0.5):1, and if the mass ratio of the glycolic acid to the ferroferric oxide is less than 0.1:1, namely, the addition amount of the glycolic acid is too small, the hydroxyl loaded on the surface layer of the macromolecular chain net in the functionalized ferroferric oxide particles is less; if the mass ratio of the glycolic acid to the ferroferric oxide is more than 0.5:1, namely, the addition amount of the glycolic acid is too much, the adsorption performance cannot be greatly improved due to the addition of too much glycolic acid due to limited loading sites, and the preparation cost is increased.
Preferably, the mass ratio of the carbon disulfide to the ferroferric oxide in the step (1) is (0.2-0.8):1, and may be, for example, 0.2:1, 0.25:1, 0.3:1, 0.35:1, 0.4:1, 0.45:1, 0.5:1, 0.55:1, 0.6:1, 0.65:1, 0.7:1, 0.75:1, 0.8:1, and the like, but not limited to the enumerated values, and other values not enumerated in the above numerical range are also applicable.
The mass ratio of the carbon disulfide to the ferroferric oxide is (0.2-0.8):1, and if the mass ratio of the carbon disulfide to the ferroferric oxide is less than 0.2:1, namely, the addition amount of the carbon disulfide is too small, the surface layer of a macromolecular chain net in functionalized ferroferric oxide particles cannot completely cover the ferroferric oxide particles; if the mass ratio of the carbon disulfide to the ferroferric oxide is more than 0.8:1, that is, if the addition amount of the carbon disulfide is too large, the preparation cost is increased.
Preferably, the mass ratio of the ammonium citrate to the ferroferric oxide in the step (1) is (0.1-0.5):1, and the mass ratio may be, for example, 0.1:1, 0.15:1, 0.2:1, 0.25:1, 0.3:1, 0.35:1, 0.4:1, 0.45:1, 0.5:1, and the like, but the ammonium citrate and the ferroferric oxide are not limited to the enumerated values, and other unrecited values in the above numerical range are also applicable.
The mass ratio of the ammonium citrate to the ferroferric oxide is (0.1-0.5):1, and if the mass ratio of the ammonium citrate to the ferroferric oxide is less than 0.1:1, namely, the addition amount of the ammonium citrate is too small, the amino or imino loaded on the surface layer of the macromolecular chain net in the functionalized ferroferric oxide particles is less; if the mass ratio of the ammonium citrate to the ferroferric oxide is more than 0.5:1, namely, the adding amount of the ammonium citrate is too much, the adding amount of the ammonium citrate is limited, so that the adsorption performance is not greatly improved, and the preparation cost is increased.
Preferably, the mass ratio of the ferroferric oxide to the solvent in the step (1) is 1 (20-100), and may be, for example, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, 1:55, 1:60, 1:65, 1:70, 1:75, 1:80, 1:85, 1:90, 1:95, 1:100, etc., but the ratio is not limited to the enumerated values, and other values not enumerated in the above numerical range are also applicable.
As a preferred technical scheme of the invention, the solvent in the step (1) comprises deionized water or an organic solvent.
Preferably, the organic solvent comprises any one of or a combination of at least two of dimethylsulfoxide, alcohols, ketones or amines, typical but non-limiting examples of which include combinations of dimethylsulfoxide and alcohols, alcohols and amines, or combinations of dimethylsulfoxide and amines.
Preferably, the alcohol comprises any one of methanol, ethanol, glycerol, ethylene glycol, n-propanol or isopropanol, or a combination of at least two of these, typical but non-limiting examples of which include a combination of methanol and ethanol, a combination of ethanol and glycerol, a combination of n-propanol and isopropanol, a combination of ethanol and ethylene glycol, or a combination of n-propanol and ethanol.
Preferably, the ketones comprise acetone and/or N-methylpyrrolidone.
Preferably, the amine comprises N, N-dimethylformamide.
As a preferable technical scheme of the invention, the mixing mode in the step (1) is ultrasonic.
Preferably, the temperature of the mixing in step (1) is 20-30 ℃, and may be, for example, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃, 30 ℃, etc., but is not limited to the recited values, and other values not recited in the above-mentioned range of values are also applicable.
Preferably, the mixing time in step (1) is 1-3h, such as 1h, 1.2h, 1.4h, 1.6h, 1.8h, 2h, 2.1h, 2.3h, 2.5h, 2.7h, 2.9h, 3h, etc., but not limited to the recited values, and other values not recited in the above range of values are also applicable.
In a preferred embodiment of the present invention, a pH adjuster is added to the suspension of step (1) to make the suspension alkaline before the reaction of step (2).
Preferably, the pH adjuster comprises any one of ammonia, sodium hydroxide or potassium hydroxide or a combination of at least two of them, typical but non-limiting examples of which include a combination of ammonia and sodium hydroxide, a combination of ammonia and potassium hydroxide, or a combination of sodium hydroxide and potassium hydroxide.
In a preferred embodiment of the present invention, the mass ratio of epichlorohydrin in the step (2) to ferroferric oxide in the step (1) is (0.05-0.45):1, and may be, for example, 0.05:1, 0.1:1, 0.15:1, 0.2:1, 0.25:1, 0.3:1, 0.35:1, 0.4:1, 0.45:1, etc., but the present invention is not limited to the above-mentioned values, and other values not listed in the above-mentioned range of values are also applicable.
The mass ratio of epichlorohydrin to ferroferric oxide is (0.05-0.45):1, and if the mass ratio of glycolic acid to ferroferric oxide is less than 0.05:1, namely, the addition amount of epichlorohydrin is too small, epoxy groups loaded on the surface layer of a macromolecular chain net in functionalized ferroferric oxide particles are reduced, and the capability of the functionalized ferroferric oxide particles for chelating heavy metals is reduced; if the mass ratio of the glycolic acid to the ferroferric oxide is greater than 0.45:1, namely, the addition amount of the epichlorohydrin is too much, and the addition of the epichlorohydrin is limited, so that the adsorption performance is not greatly improved, and the preparation cost is increased.
Preferably, the epichlorohydrin is added in step (2) at a rate of 0.1-0.2mL/min, such as 0.1mL/min, 0.11mL/min, 0.12mL/min, 0.13mL/min, 0.14mL/min, 0.15mL/min, 0.16mL/min, 0.17mL/min, 0.18mL/min, 0.19mL/min, 0.2mL/min, but not limited to the values listed, and other values not listed in the above range of values are equally applicable.
Preferably, the reaction temperature in step (2) is 40-100 deg.C, such as 40 deg.C, 42 deg.C, 45 deg.C, 48 deg.C, 50 deg.C, 52 deg.C, 55 deg.C, 57 deg.C, 60 deg.C, 63 deg.C, 65 deg.C, 68 deg.C, 70 deg.C, 72 deg.C, 75 deg.C, 77 deg.C, 80 deg.C, 83 deg.C, 85 deg.C, 88 deg.C, 90 deg.C, 92 deg.C, 95 deg.C, 97 deg.C, 100 deg.C, etc., but it is not limited to the values listed, and other values not listed in the above range are also applicable.
The preferable reaction temperature is 40-100 ℃, if the reaction temperature is lower than 40 ℃, the reaction of the raw material components is insufficient, the functionalized ferroferric oxide particles can not be obtained, and the adsorption effect is poor; if the temperature is higher than 100 ℃, the polymer chains are broken, the surface area of the material is greatly reduced, and the removal rate of heavy metal ions is reduced.
Preferably, before the reaction in step (2), the suspension is heated to the reaction temperature, and then epichlorohydrin is added dropwise for reaction.
Preferably, the reaction time in step (2) is 2-4h, such as 2h, 2.2h, 2.5h, 2.8h, 3h, 3.2h, 3.5h, 3.8h, 4h, etc., but not limited to the recited values, and other values not recited in the above range of values are also applicable.
As a preferable technical scheme of the invention, the solid-liquid separation mode in the step (2) is vacuum filtration.
Preferably, the washing manner in step (2) is that the washing is performed by using distilled water and then ethanol.
Preferably, the drying mode in the step (2) is vacuum drying.
Preferably, the drying temperature in step (2) is 40-100 deg.C, such as 40 deg.C, 42 deg.C, 45 deg.C, 48 deg.C, 50 deg.C, 52 deg.C, 55 deg.C, 57 deg.C, 60 deg.C, 63 deg.C, 65 deg.C, 68 deg.C, 70 deg.C, 72 deg.C, 75 deg.C, 77 deg.C, 80 deg.C, 83 deg.C, 85 deg.C, 88 deg.C, 90 deg.C, 92 deg.C, 95 deg.C, 97 deg.C, 100 deg.C, etc., but it is not limited to the recited values, and other values in the above range are also applicable.
Preferably, the drying time in step (2) is 2-6h, such as 2h, 2.2h, 2.5h, 2.8h, 3h, 3.2h, 3.5h, 3.8h, 4h, 4.2h, 4.5h, 4.8h, 5h, 5.3h, 5.5h, 5.8h, 6h, etc., but not limited to the recited values, and other values in the above range are also applicable.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) mixing ferroferric oxide, glycolic acid, carbon disulfide and ammonium citrate with a solvent according to the mass ratio of 1 (0.1-0.5) to (0.2-0.8) to (0.1-0.5), and performing ultrasonic treatment at 20-30 ℃ for 1-3h to obtain a suspension;
the mass ratio of the ferroferric oxide to the solvent is 1 (20-100), the solvent comprises deionized water or an organic solvent, the organic solvent comprises any one or the combination of at least two of dimethyl sulfoxide, alcohols, ketones or amines, the alcohols comprise any one or the combination of at least two of methanol, ethanol, glycerol, ethylene glycol, N-propanol or isopropanol, the ketones comprise acetone and/or N-methylpyrrolidone, and the amines comprise N, N-dimethylformamide;
(2) adding a pH regulator to regulate the suspension liquid in the step (1) to be alkaline, heating to 40-100 ℃, dropwise adding epoxy chloropropane at the speed of 0.1-0.2mL/min, reacting at 40-100 ℃ for 2-4h, carrying out vacuum filtration and washing, and carrying out vacuum drying at 40-100 ℃ for 2-6h to obtain functionalized ferroferric oxide particles;
the mass ratio of the epichlorohydrin to the ferroferric oxide is (0.05-0.45):1, and the washing mode is that the epichlorohydrin and the ferroferric oxide are washed by distilled water and then by ethanol.
The third purpose of the invention is to provide application of the functionalized ferroferric oxide particles obtained by the preparation method for one purpose or the second purpose, wherein the functionalized ferroferric oxide particles are used for treating heavy metal wastewater.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
(1) the functionalized ferroferric oxide particle disclosed by the invention has a chelation functional surface layer and a ferroferric oxide core at the same time, and has excellent heavy metal chelation and trapping capacity and excellent magnetic separation performance;
(2) the surface of the functionalized ferroferric oxide particle is a polymer chain network, so that the magnetic property cannot be weakened due to the over-thick coating layer, the functionalized ferroferric oxide particle is easy to separate, and the recovery operation is simple and convenient;
(3) the preparation method of the functionalized ferroferric oxide particles is simple and is beneficial to industrial popularization and application.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides functionalized ferroferric oxide particles and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) mixing ferroferric oxide, glycolic acid, carbon disulfide and ammonium citrate with deionized water according to the mass ratio of 1:0.3:0.4:0.3, controlling the mass ratio of the ferroferric oxide to the deionized water to be 1:50, and carrying out ultrasonic treatment at 25 ℃ for 2 hours to obtain a suspension;
(2) adding sodium hydroxide to adjust the suspension liquid in the step (1) to be alkaline, heating to 75 ℃, dropwise adding epoxy chloropropane at the speed of 0.15mL/min, reacting for 3h at 75 ℃, vacuum-filtering and washing, and vacuum-drying for 4h at 75 ℃ to obtain functionalized ferroferric oxide particles; wherein the mass ratio of the epichlorohydrin to the ferroferric oxide is 0.25: 1.
Example 2
The embodiment provides functionalized ferroferric oxide particles and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) mixing ferroferric oxide, glycolic acid, carbon disulfide and ammonium citrate with deionized water according to the mass ratio of 1:0.1:0.2:0.1, controlling the mass ratio of the ferroferric oxide to the deionized water to be 1:20, and carrying out ultrasonic treatment at 20 ℃ for 3 hours to obtain a suspension;
(2) adding sodium hydroxide to adjust the suspension liquid in the step (1) to be alkaline, heating to 40 ℃, dropwise adding epoxy chloropropane at the speed of 0.1mL/min, reacting for 4 hours at 40 ℃, vacuum-filtering and washing, and vacuum-drying for 6 hours at 40 ℃ to obtain functionalized ferroferric oxide particles; wherein the mass ratio of the epichlorohydrin to the ferroferric oxide is 0.05: 1.
Example 3
The embodiment provides functionalized ferroferric oxide particles and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) mixing ferroferric oxide, glycolic acid, carbon disulfide and ammonium citrate with absolute ethyl alcohol according to the mass ratio of 1:0.5:0.8:0.5, controlling the mass ratio of the ferroferric oxide to the absolute ethyl alcohol to be 1:100, and carrying out ultrasonic treatment at 30 ℃ for 1 hour to obtain a suspension;
(2) adding sodium hydroxide to adjust the suspension liquid in the step (1) to be alkaline, heating to 100 ℃, dropwise adding epoxy chloropropane at the speed of 0.2mL/min, reacting at 100 ℃ for 3 hours, carrying out vacuum filtration and washing, and carrying out vacuum drying at 100 ℃ for 2 hours to obtain functionalized ferroferric oxide particles; wherein the mass ratio of the epichlorohydrin to the ferroferric oxide is 0.45: 1.
Example 4
This example provides a functionalized ferroferric oxide particle and a preparation method thereof, except that the mass ratio of the ferroferric oxide, the glycolic acid, the carbon disulfide and the ammonium citrate in the step (1) is changed from 1:0.3:0.4:0.3 to 1:0.05:0.4:0.3, and other conditions are the same as those in example 1.
Example 5
This example provides a functionalized ferroferric oxide particle and a preparation method thereof, except that the mass ratio of the ferroferric oxide, the glycolic acid, the carbon disulfide and the ammonium citrate in the step (1) is replaced by 1:0.3:0.4:0.3 to 1:0.7:0.4:0.3, and the other conditions are the same as those in the example 1.
Example 6
This example provides a functionalized ferroferric oxide particle and a preparation method thereof, except that the mass ratio of the ferroferric oxide, the glycolic acid, the carbon disulfide and the ammonium citrate in the step (1) is changed from 1:0.3:0.4:0.3 to 1:0.3:0.1:0.3, and other conditions are the same as those in example 1.
Example 7
This example provides a functionalized ferroferric oxide particle and a preparation method thereof, except that the mass ratio of the ferroferric oxide, the glycolic acid, the carbon disulfide and the ammonium citrate in the step (1) is changed from 1:0.3:0.4:0.3 to 1:0.3:0.9:0.3, and other conditions are the same as those in example 1.
Example 8
This example provides a functionalized ferroferric oxide particle and a preparation method thereof, except that the mass ratio of the ferroferric oxide, the glycolic acid, the carbon disulfide and the ammonium citrate in the step (1) is changed from 1:0.3:0.4:0.3 to 1:0.3:0.4:0.05, and the other conditions are the same as those in the example 1.
Example 9
This example provides a functionalized ferroferric oxide particle and a preparation method thereof, except that the mass ratio of the ferroferric oxide, the glycolic acid, the carbon disulfide and the ammonium citrate in the step (1) is changed from 1:0.3:0.4:0.3 to 1:0.3:0.4:0.7, and other conditions are the same as those in example 1.
Example 10
This example provides functionalized ferroferric oxide particles and a preparation method thereof, except that the mass ratio of epichlorohydrin to ferroferric oxide in the step (2) is changed from 0.25:1 to 0.01:1, and the other conditions are exactly the same as those in example 1.
Example 11
This example provides functionalized ferroferric oxide particles and a preparation method thereof, except that the mass ratio of epichlorohydrin to ferroferric oxide in the step (2) is changed from 0.25:1 to 0.55:1, and the other conditions are exactly the same as those in example 1.
Example 12
This example provides a functionalized ferroferric oxide particle and a preparation method thereof, except that the temperature of the reaction in the step (2) is changed from 75 ℃ to 35 ℃, and the conditions are the same as those in the example 1.
Example 13
This example provides a functionalized ferroferric oxide particle and a preparation method thereof, except that the temperature of the reaction in the step (2) is changed from 75 ℃ to 110 ℃, and the conditions are the same as those in the example 1.
Comparative example 1
The present comparative example provides a functionalized ferroferric oxide particle and a method for preparing the same, which are described with reference to example 1, except that: omitting the glycolic acid of step (1); the specific content of the step (1) is as follows:
(1) mixing ferroferric oxide, carbon disulfide and ammonium citrate with deionized water according to the mass ratio of 1:0.4:0.3, controlling the mass ratio of the ferroferric oxide to the deionized water to be 1:20, and carrying out ultrasonic treatment at 20 ℃ for 3 hours to obtain suspension.
Comparative example 2
The present comparative example provides a functionalized ferroferric oxide particle and a method for preparing the same, which are described with reference to example 1, except that: omitting the carbon disulfide of step (1); the specific content of the step (1) is as follows:
(1) mixing ferroferric oxide, glycolic acid and ammonium citrate with deionized water according to the mass ratio of 1:0.3:0.3, controlling the mass ratio of the ferroferric oxide to the deionized water to be 1:20, and carrying out ultrasonic treatment at 20 ℃ for 3 hours to obtain suspension.
Comparative example 3
The present comparative example provides a functionalized ferroferric oxide particle and a method for preparing the same, which are described with reference to example 1, except that: omitting the ammonium citrate of step (1); the specific content of the step (1) is as follows:
(1) mixing ferroferric oxide, glycolic acid and carbon disulfide with deionized water according to the mass ratio of 1:0.3:0.4, controlling the mass ratio of the ferroferric oxide to the deionized water to be 1:50, and carrying out ultrasonic treatment at 25 ℃ for 2 hours to obtain suspension;
comparative example 4
The present comparative example provides a functionalized ferroferric oxide particle and a method for preparing the same, which are described with reference to example 1, except that: omitting the epichlorohydrin in the step (2); the specific content of the step (2) is as follows:
(2) and (2) adding sodium hydroxide to adjust the suspension liquid in the step (1) to be alkaline, heating to 80 ℃ to react for 3 hours, carrying out vacuum filtration and washing, and carrying out vacuum drying at 80 ℃ for 4 hours to obtain the functionalized ferroferric oxide particles.
The functionalized ferroferric oxide particles obtained in the above examples and comparative examples are subjected to heavy metal adsorption tests, and the test steps are as follows:
adding 50mg of functionalized ferroferric oxide particles into 10mL of heavy metal wastewater with the concentration of 0.1mol/L, adsorbing for 30min under the irradiation of 365nm ultraviolet lamp light, testing the absorbance of the heavy metal wastewater before and after illumination, and calculating to obtain the removal rate of the functionalized ferroferric oxide particles to the heavy metal ions; wherein the heavy metal wastewater respectively contains Cd2+、Pd2+、Co2+、Ni2+、Cu2+Or Pb2+Wastewater containing heavy metal ions.
The functionalized ferroferric oxide particle pair Cd obtained in the above examples and comparative examples2+、Pd2+、Co2+、Ni2+、Cu2+、Pb2+The removal rates of the six heavy metal ions are shown in table 1.
TABLE 1
The following points can be derived from table 1:
(1) from examples 1 to 3, it can be seen that, in the preferred range of the present invention, the functionalized ferroferric oxide particles have excellent ability of chelating and trapping heavy metals, and the present invention uniformly mixes ferroferric oxide, glycolic acid, carbon disulfide and ammonium citrate with a solvent, effectively increases active functional groups on the functionalized ferroferric oxide particles, and significantly improves the adsorption effect of the product on heavy metal ions;
(2) comparing example 1 with examples 4 to 11, it can be found that if the content of any one raw material component in glycolic acid, carbon disulfide, ammonium citrate or epichlorohydrin is insufficient, the adsorption performance of the functionalized ferroferric oxide particles is reduced, and the removal rate of metal ions is reduced; if the content of any raw material component in the glycolic acid, the carbon disulfide, the ammonium citrate or the epichlorohydrin is too much, due to limited reaction sites, the functionalized ferroferric oxide particles cannot have better adsorption performance, but the raw materials are wasted, and the preparation cost is increased;
(3) comparing example 1 with examples 12 and 13, it can be seen that, since the reaction temperature in example 12 is 35 ℃ which is lower than the preferred temperature of 40 to 100 ℃ in the present invention, the reaction of each raw material component is insufficient, which leads to the decrease of the adsorption performance; since the reaction temperature in example 13 is 110 ℃ which is higher than the preferable temperature of 40-100 ℃ in the invention, part of the polymer chains are broken, the surface area of the material is reduced, and the removal rate of heavy metal ions is reduced;
(4) comparing example 1 with comparative examples 1 to 4, it can be seen that, when glycolic acid is omitted as a raw material component, the adsorption performance of the functionalized ferroferric oxide particles is obviously reduced because no hydroxyl group exists on the surface layer of the polymer chain network in the functionalized ferroferric oxide particles; when the carbon disulfide is omitted as a raw material component, the adsorption performance of the functionalized ferroferric oxide particles is obviously reduced, because the polymer chain net surface layer of the functionalized ferroferric oxide particles cannot completely cover the ferroferric oxide particles, the functional groups loaded on the polymer chain net surface layer of the functionalized ferroferric oxide particles are reduced; when the ammonium citrate is omitted, the adsorption performance of the functionalized ferroferric oxide particles is obviously reduced, because no amino or imino is on the surface layer of the macromolecular chain net in the functionalized ferroferric oxide particles; when the raw material component of epichlorohydrin is omitted, the adsorption performance of the functionalized ferroferric oxide particles is obviously reduced and the reduction degree is larger, because the epoxy group is a group for chelating metal ions and is the key for improving the adsorption capacity of heavy metals.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A functionalized ferroferric oxide particle is characterized in that the functionalized ferroferric oxide particle consists of a magnetic ferroferric oxide core and a polymer chain net surface layer; the active groups on the surface layer of the macromolecular chain net comprise hydroxyl, amino, imino and epoxy.
2. A method for preparing functionalized ferroferric oxide particles according to claim 1, wherein the method comprises the following steps:
(1) mixing ferroferric oxide, glycolic acid, carbon disulfide, ammonium citrate and a solvent to obtain a suspension;
(2) and (2) dropwise adding epoxy chloropropane into the suspension obtained in the step (1) to react, and sequentially carrying out solid-liquid separation, washing and drying to obtain functionalized ferroferric oxide particles.
3. The method for preparing functionalized ferroferric oxide particles according to claim 2, wherein the mass ratio of the glycolic acid to the ferroferric oxide in the step (1) is (0.1-0.5): 1;
preferably, the mass ratio of the carbon disulfide to the ferroferric oxide in the step (1) is (0.2-0.8): 1;
preferably, the mass ratio of the ammonium citrate to the ferroferric oxide in the step (1) is (0.1-0.5): 1;
preferably, the mass ratio of the ferroferric oxide to the solvent in the step (1) is 1 (20-100).
4. The method for preparing functionalized ferroferric oxide particles according to claim 2 or 3, wherein the solvent in the step (1) comprises deionized water or an organic solvent;
preferably, the organic solvent comprises any one or a combination of at least two of dimethyl sulfoxide, alcohols, ketones or amines;
preferably, the alcohol comprises any one of methanol, ethanol, glycerol, ethylene glycol, n-propanol or isopropanol or a combination of at least two of the same;
preferably, the ketones comprise acetone and/or N-methylpyrrolidone;
preferably, the amine comprises N, N-dimethylformamide.
5. The method for preparing functionalized ferroferric oxide particles according to any one of claims 2-4, wherein the mixing in the step (1) is ultrasonic;
preferably, the temperature of the mixing in the step (1) is 20-30 ℃;
preferably, the mixing time of step (1) is 1-3 h.
6. The method for preparing functionalized ferroferric oxide particles according to any one of claims 2-5, wherein a pH regulator is added to adjust the suspension liquid in the step (1) to be alkaline before the reaction in the step (2);
preferably, the pH adjuster comprises any one of ammonia, sodium hydroxide or potassium hydroxide or a combination of at least two thereof.
7. The method for preparing functionalized ferroferric oxide particles according to any one of claims 2 to 6, wherein the mass ratio of the epichlorohydrin in the step (2) to the ferroferric oxide in the step (1) is (0.05-0.45): 1;
preferably, the dripping speed of the epichlorohydrin in the step (2) is 0.1-0.2 mL/min;
preferably, the temperature of the reaction of the step (2) is 40-100 ℃;
preferably, before the reaction in the step (2), the suspension is heated to the reaction temperature, and then epichlorohydrin is added dropwise for reaction;
preferably, the reaction time of step (2) is 2-4 h.
8. The preparation method of the functionalized ferroferric oxide particles according to any one of claims 2 to 7, wherein the solid-liquid separation in the step (2) is vacuum filtration;
preferably, the washing mode of the step (2) is to wash with distilled water firstly and then wash with ethanol;
preferably, the drying mode in the step (2) is vacuum drying;
preferably, the temperature for drying in the step (2) is 40-100 ℃;
preferably, the drying time of the step (2) is 2-6 h.
9. The preparation method of the functionalized ferroferric oxide particles according to any one of claims 2 to 8, wherein the preparation method comprises the following steps:
(1) mixing ferroferric oxide, glycolic acid, carbon disulfide and ammonium citrate with a solvent according to the mass ratio of 1 (0.1-0.5) to (0.2-0.8) to (0.1-0.5), and performing ultrasonic treatment at 20-30 ℃ for 1-3h to obtain a suspension;
the mass ratio of the ferroferric oxide to the solvent is 1 (20-100), the solvent comprises deionized water or an organic solvent, the organic solvent comprises any one or the combination of at least two of dimethyl sulfoxide, alcohols, ketones or amines, the alcohols comprise any one or the combination of at least two of methanol, ethanol, glycerol, ethylene glycol, N-propanol or isopropanol, the ketones comprise acetone and/or N-methylpyrrolidone, and the amines comprise N, N-dimethylformamide;
(2) adding a pH regulator to regulate the suspension liquid in the step (1) to be alkaline, heating to 40-100 ℃, adding epichlorohydrin dropwise at the speed of 0.1-0.2mL/min by using the pH regulator comprising any one or the combination of at least two of ammonia water, sodium hydroxide or potassium hydroxide, reacting at 40-100 ℃ for 2-4h, carrying out vacuum filtration and washing, and carrying out vacuum drying at 40-100 ℃ for 2-6h to obtain functionalized ferroferric oxide particles;
the mass ratio of the epichlorohydrin to the ferroferric oxide is (0.05-0.45):1, and the washing mode is that the epichlorohydrin and the ferroferric oxide are washed by distilled water and then by ethanol.
10. Use of the functionalized ferroferric oxide particles according to claim 1 or obtained by the preparation method of any one of claims 2 to 9, wherein the functionalized ferroferric oxide particles are used for treating heavy metal wastewater.
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